JPH02141594A - Method and device for forming high-purity metallic cylindrical body - Google Patents

Abstract

PURPOSE:To deposit an extremely high-purity metal around a revolving shaft of a cathode and to produce a cylindrical body consisting of the high-purity metal for production of a superconducting wire by putting an electrolyte contg. metal ions into an electrolytic cell, immersing consumable anodes and the cathode consisting of the revolving shaft therein and energizing the two electrodes while revolving the cathode. CONSTITUTION:The electrolyte consisting of an aq. soln. contg. copper sulfate and sulfuric acid is put into the electrolytic cell 2 and the consumable anodes 5, 5 consisting of copper plates and the cathode consisting of the revolving shaft 4 made of Ti are immersed therein. A DC voltage is applied between the cathode 4 and the anode 5 by a power source P to energize the two electrodes and while the Cu ions are replenished by dissolving the copper plates of the consumable anode 5, the copper D having the extremely high purity is deposited at a uniform thickness around the Ti revolving shaft 4 which is the cathode. The cathode is taken out of the electrolyte when the deposited copper D grows to a prescribed thickness. The deposited copper is then pulled from the revolving shaft 4 and the cylindrical body of the Cu having the extremely high purity for production of the superconducting wire is thus produced.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. The present invention relates to an apparatus for forming a metal cylindrical body such as a metal pipe, and particularly relates to an apparatus for forming a metal cylindrical body such as a metal pipe. The present invention relates to a method and apparatus for forming a high-purity metal cylindrical body, which forms a cylindrical body of extremely high purity metal that can be used as a stabilizing material for superconducting wires.

Traditionally, for example, when manufacturing superconducting wire, a superconducting alloy made of titanium, niobium, tin, etc. is composited into a high-purity metal pipe such as a high-purity Cu pipe to create a wire. A large number of strands of wire are bundled and then filled into a high-purity metal pipe such as a high-purity Cu pipe, which is then manufactured into a predetermined size by extrusion or drawing. In this way, high-purity metal pipes such as high-purity Cu pipes used in manufacturing superconducting wires are able to shunt the flowing current to the high-purity metal even if part of the superconducting wire transitions to normal conductivity. Therefore, this high-purity metal pipe is used as a stabilizing material for superconducting wires, and the metal used in it does not contain any impurities. Extremely high purity is required.

Until now, such high-purity metal pipes have been produced by melting metal such as high-purity Cu and pouring it into a predetermined cast base, or by melting high-purity metal such as Cu in a "crucible". Metal is melted and cooled to form a metal lump, then the peripheral part or center is cut into a cylindrical shape, and then it is made into a pipe shape using an extrusion machine etc. to make a metal pipe, or it is forged. A metal pipe was produced by rolling a metal plate obtained by rolling and then welding the joints to form a pipe.

However, the conventional technology described above requires a process of melting high-purity metal, and at this time, the high-purity metal produced by the work accompanying the melting process or from the "crucible" etc. used in the melting process. Iron (Fe), silver (Ag) to the pipe
) or impurities such as sulfur (S) could not be avoided. When such impurity infiltration occurs, 3R (Res) as a stabilizing material for superconducting wires is affected by the impurity.
The residual resistance value, that is, the residual resistance value, decreases significantly, which impedes the use of this high-purity metal pipe as a stabilizing material for superconducting wires. Therefore, in order to melt high-purity metal and create high-purity metal pipes without contamination with impurities,
High-purity metals had to be cast in a vacuum, or high-purity crucibles had to be used, requiring special equipment and equipment.

Therefore, the present invention has been made in view of the above points, and its purpose is to eliminate the need for a melting process and to use special equipment and equipment such as a vacuum state or a high-purity crucible. To provide a method for forming a high-purity metal cylindrical body and an apparatus therefor, which can simply and easily produce a high-purity metal cylindrical body used for superconducting wires, etc., without introducing contamination from impurities. That's true.

Therefore, the above objects are achieved by the method and apparatus for forming a high-purity metal cylinder according to the present invention. In summary, the present invention:
A rotating shaft is rotatably supported as a cathode in an electrolytic cell filled with an electrolytic solution, and a metal to be electrodeposited is placed as an anode.
rotating the rotating shaft at a predetermined speed; applying current at a predetermined current density between the rotating shaft and the electrodeposited metal; and applying the electrodeposited metal to a predetermined thickness on the rotating rotating shaft in a cylindrical manner. When the electrodeposited metal has been electrodeposited to a predetermined thickness on the rotating shaft, the rotating shaft is taken out from the electrolytic bath 5, and only the electrodeposited metal portion is deposited on the rotating shaft. A method for forming a high-purity metal cylindrical body comprising the steps of pulling it out from the electrolyte, an electrolytic tank containing an electrolyte, a cathode rotating shaft at least partially immersed in the electrolyte and driven to rotate, and a cathode rotating shaft that is immersed and serves as an anode. The electrodeposited metal to be used, a rotating shaft support means for supporting the rotating shaft, a rotation driving means for rotating the rotating shaft, and a power source for supplying current between the rotating shaft and the electrodeposited metal. A high-purity metal cylindrical body forming apparatus comprising:

EMBODIMENT OF THE INVENTION Hereinafter, the present invention will be explained based on one embodiment with reference to the accompanying drawings.

First, before describing embodiments of the present invention, the principle of the present invention will be explained with reference to FIG. FIG. 1 shows a principle diagram of a high-purity metal cylindrical body forming apparatus 1 according to the present invention.
A rotating shaft 4 serving as a cathode connected to the negative pole of a power source P via a sliding electrode 3 is disposed inside the electrolytic cell 2, and a rotating shaft 4 is arranged at a slight distance from the rotating shaft 4. A pair of copper plates 5, which are electrodeposited metals, are arranged as anodes connected to the positive electrode of the power source P. Here, the term "electrodeposited metal" refers to a metal used as an anode such that the copper plate 5 serving as the anode is melted by electrolysis and deposited and electrodeposited on the rotating shaft 4 serving as the cathode.

The rotating shaft 4 is removably connected to and fixed to a rotational drive section 8 via a connection section 7 having an insulating member 6 at one end side that is not immersed in the electrolytic bath 2 . The rotational driving force from the rotary shaft 4 is accurately transmitted to the rotating shaft 4.

The other end of the rotating shaft 4 is slightly spaced apart from the bottom plate of the electrolytic cell 2 so that it can freely rotate within the electrolytic cell 2. A predetermined amount of electrolytic solution prepared in this manner is filled.

The high-purity metal cylindrical body forming apparatus of the present invention configured as described above energizes the rotating shaft 4 as a cathode and the copper plate 5 as an anode at a predetermined current density from the power source P, and operates the rotation drive unit 8. transmitting the rotational driving force from the rotational drive unit 8 to the rotating shaft 4 via the connecting unit 7 having the insulating member 6;
The rotating shaft 4 is rotated at a predetermined number of rotations.

At this time, in the electrolytic tank 2 filled with the electrolytic solution, electrolysis occurs according to the principle of electrolysis when electricity is applied, and the copper plate 5 of the anode as the electrodeposited metal is dissolved, and the rotating shaft 4 of the cathode is dissolved. , copper from the copper plate 5 of the anode precipitates and adheres,
In other words, it is electrodeposited. At this time, since the rotating shaft 4 is rotating, the precipitated copper paste can be uniformly adhered to the surface of the rotating shaft 4. In this way, the precipitated copper paste adheres to the rotating shaft 4, and this precipitated copper paste is formed into a cylindrical shape around the rotating shaft 4, and the precipitated copper paste deposited on the surface of the rotating shaft 4 is
Copper plate 5 as electrodeposited metal initially used as an anode
The purity is much higher than that of . That is, electrolytic refining is performed by depositing and electrodepositing high-purity precipitated metal, ie, precipitated copper, on the rotating shaft of the cathode from the copper plate of the anode, which is used as a low-purity electrodeposited metal.

The deposited copper paste on the rotating shaft 4 obtained in this way is removed by separating the rotating shaft 4 from the connecting part 7, and then fixing only the deposited copper paste on the rotating shaft 4 with a tool or the like, and then pulling out the rotating shaft 4. As a result, a cylindrical deposited copper alloy is obtained in which the rotating shaft 4 portion is hollow. At this time, in order to facilitate the extraction of the deposited copper paste from the rotating shaft 4, it is preferable to previously apply a soap solution or the like to the surface of the rotating shaft 4 prior to the electrolytic refining described above.

Hereinafter, one embodiment of the present invention will be described with reference to FIG.

FIG. 2 is a partially cutaway schematic perspective view of an embodiment of the high-purity metal cylinder forming apparatus according to the present invention. It is provided with an outer tank 11 having a shape and an inner tank 12 as a rectangular electrolytic tank housed in the outer tank 11, and the outer tank 11 is placed on a base A. The inner tank 12 is housed in the outer tank 11 as shown in FIG.
11, and is accommodated in the outer tank 11 with its longitudinal direction aligned with the longitudinal direction of the outer tank 11. At this time, the inner tank 12 has a pair of holes on both ends of the outer bottom. The inner tank 12 has legs 13, and the inner tank 12 is accommodated in the outer tank 11 with a slight distance from the bottom plate of the outer tank 11.

Both side walls 14 of the outer layer 11 are perpendicular to the longitudinal direction of the outer tank 11, and both side walls 15 of the inner layer 12 are perpendicular to the longitudinal direction of the inner tank 12.
, are provided with vertically elongated slits 16 and 17, which are open at the top, at a preferable height above the bottoms of the outer tank 11 and the inner tank 12, respectively, at approximately the center thereof. Both side walls 14
．． These slits 16,17 provided in 15 coincide along the longitudinal direction of the outer tank 11 and the inner tank 12.

Therefore, it is inserted from above the pickpockets 1) 16.17, and slightly spaced from the sides of these pickpockets 1) 16.17.
And through these slits, the inside of the inner tank 12 and the inside of the outer tank 1
It is possible to arrange the rotating shaft 18 so as to pass through the outer tank 1, and the arranged rotating shaft 18 is arranged at both outer ends of the outer tank 11 in the longitudinal direction of the outer tank 11. It is supported by a pair of bearings 19 as rotating shaft support means. These bearings 19 are removably fixed on a bearing mounting table 20 set at a suitable height, and this bearing mounting table 20 is fixed on the base A described above. Note that the rotating shaft 18 is made of titanium in this embodiment.

A pulley 21 is attached to one end of the rotating shaft 18 that is supported by a pair of bearings 19 and protrudes from the bearings 19. This pulley 21 is connected to a motor as a rotational drive means via a belt 22 made of an insulating material. It is connected to a pulley 24 mounted on a rotating shaft 23. Therefore, the rotational driving force of the motor 23 is transmitted to the rotating shaft 18 via the pulley 24, belt 22, and pulley 21.

On the other end side of the rotating shaft 18 protruding from the bearing 19,
A brush 25 is attached that comes into contact with the rotating shaft 18 and is connected to the negative side of the electric wire 8F. In addition, at this time, the rotating shaft 1
The belt 22 on one end side of the belt 8 is an insulating collar. Therefore, the rotating shaft 18 will be used as a cathode.

In addition, when the deposited copper deposited on the rotating shaft 18 grows due to electrolytic refining and is exposed on the electrolyte surface, the deposited copper becomes like a water wheel and scatters the electrolyte. Inner tank 1 can be submerged under the electrolyte surface to increase the current and improve the productivity of deposited copper.
After inserting a slit plate 17' into the slit 17 of the inner tank 12, a predetermined amount of electrolyte is filled in the slit 17 of the inner tank 12 so as to prevent the electrolyte in the inner tank 2 from flowing out.
Four (in this example, two sheets are shown) copper plates 26 as electrodeposited metals (in this example, copper has a purity of 99).
．． (99% of them are used) are erected apart from the rotating shaft 18 so as not to come into contact with the rotating shaft 18,
This copper plate 26 is connected to the positive side of the power supply P. Therefore, the copper plate 26 will be used as an anode. In addition, the electrolytic solution mentioned above contains sulfuric acid (HzSO4) or nitric acid (Hz N03) at a concentration of 80g/liter to 120g.
/ fL, 30 to 50 g/fL of copper (Cu) is dissolved to make an electrolytic solution (in this example, sulfuric acid (H
2304) to 100 g/l and 40 g/l of copper (Cu).
), the electrolysis temperature was approximately 20
degree to 60 degrees (approximately 40 degrees in this embodiment).

Note that the electrolyte level in the inner layer 12 is provided with a number of weirs (holes) 29 to keep the liquid level constant, and the electrolyte flowing out from these weirs flows between the outer tank 11 and the inner tank 12, and is then discharged. It is introduced into the tank 30 through a pipe 31 and can be circulated to the inner tank 12 through a pump 32.

Therefore, the gap between the sleeve 17 and the rotating shaft 18 and the gap between the side wall 15 of the inner tank 12 and the flange 27 are as follows:
As a result, the slit 17 is closed by the flange 27, and the electrolyte filled in the inner tank 12 only flows out into the outer tank 11 very little. .

At this time, even if the rotating shaft 18 rotates, the rotating shaft 18 and the flange 27 attached thereto and rotating integrally are separated from the slit 17 and the side wall 15, so the rotating shaft 18 comes into contact with the slit 17 and the side wall 15. Rotation is not obstructed.

The operation of the high-purity metal cylindrical body forming apparatus of the present invention configured as described above will be described below.

Now, when the high-purity metal cylindrical body forming apparatus of the present invention is in operation, the anode copper plate 26 (purity 99.99
9%) and 80 to 120 A/rn' to the rotating shaft 18 of the cathode.
A current having a current density of (100 A/m' in this embodiment) is applied, and the rotational driving force of the motor 23 is applied to the pulley 24. Transmission is made via the belt 22 and pulley 21 to rotate the rotating shaft 18 at 150 to 250 rpm (200 rpm in this embodiment).
pm). Note that at this time, a soap solution or the like is applied to the surface of the rotating shaft 18 as a mold release agent.

Then, due to the principle of electrolysis, the copper plate 26 of the anode is melted, and copper from the copper plate 26 of the anode is precipitated and attached, that is, electrodeposited, on the titanium rotating shaft 18. At this time, since the rotating shaft 18 rotates once, the precipitated copper paste can be uniformly adhered to the surface of the rotating shaft 18. In this way, the precipitated copper paste is deposited on the rotating shaft 18, and this precipitated copper paste is deposited and formed in a cylindrical shape around the rotating shaft 18 to a predetermined thickness, for example, 65 mm. The copper deposited on the surface has a purity considerably higher than the 99.99% purity of the copper plate 26 as the electrodeposited metal initially used as the anode.

The analytical values of the cylindrical copper deposits formed around the rotating shaft 18 in this manner are shown in Table 1 below for two samples.

Table 1 As seen from this Table 1, sulfur (S), silver (A g) and iron (Fe) were contained in the two samples, respectively.
The content of impurities is extremely small in ppm units, and it is possible to obtain a cylindrical precipitated copper with very high purity, that is, with high purity.

The obtained cylindrical deposited copper paste can be removed from the bearing 19 by separating the bearing 19 from the bearing mounting table 20.
and the outer tank 11 through the slit 16 and 17 together with the rotating shaft 18.
and taken out from the inner tank 12. Thereafter, the bearing 19 is removed from the rotating shaft 18, and only the cylindrical deposited copper paste on the rotating shaft 18 is fixed to a pulling device as a means for pulling out the rotating shaft, and when the rotating shaft 18 is pulled out, the rotating shaft 18 is pulled out. Only the desired cylindrical deposited copper is obtained.

This cylindrical deposited copper is passed through a pultrusion molding machine or the like, and is elongated and formed into a pipe shape, thereby forming a high-purity Cu pipe used as a stabilizing material for superconducting wires.

As mentioned above, in this example, when producing a high-purity Cu pipe used as a stabilizing material for superconducting wires, the cylindrical metal is directly obtained by electrolysis, so conventionally,
There is no need for the high-temperature melt casting that has been used, and since no crucible is used, there is no contamination of impurities from the crucible. Furthermore, since the process is shorter than conventional processes, high-purity Cu pipes can be manufactured at lower cost.

In addition, although the above-mentioned example described the case where copper (Cu) was used for the anode, the present invention is not limited to this, and any metal that can be electrolytically refined can be used as the electrodeposited metal for the anode. Even in that case, a highly pure cylindrical precipitated metal can be obtained on the rotating shaft.

Furthermore, although the present invention has been described with respect to a horizontal type high-purity metal cylindrical body forming apparatus in the above embodiment, the present invention is not limited to this embodiment. It can also be applied to mold types.

11 Differential difference 1 As explained above, according to the method and apparatus for forming a high-purity metal cylindrical body of the present invention, by using electrolysis, a high-purity precipitated metal is uniformly deposited on a rotating shaft. By pulling out the rotating shaft from this precipitated metal, a high-purity precipitated metal formed in a cylindrical shape can be obtained directly, without using a high-temperature melting process and in a vacuum state. Alternatively, there is no need for special equipment or equipment such as a high-purity crucible, and therefore, high-purity metal cylindrical bodies can be easily and easily produced without introducing impurities during the melting process or the use of crucibles. It has the advantage that it can be manufactured.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram for explaining the method of forming a high-purity metal cylinder according to the present invention. FIG. 2 is a partially cutaway schematic perspective view of an embodiment of an apparatus for forming a high-purity metal cylinder according to the present invention. 2.12: Electrolytic cell 4.18: Rotating shaft 5.26: Copper plate 8.23: Rotation drive means 19: Bearing 20: Bearing mounting table 21.24: Pulley 22: Belt D: Deposited copper L: Electrolyte P: power supply

Claims (1)

[Scope of Claims] 1) A rotary shaft is rotatably supported as a cathode in an electrolytic cell filled with an electrolytic solution, and an electrodeposited metal is placed as an anode, and the rotary shaft is rotated at a predetermined speed. , applying current at a predetermined current density between the rotating shaft and the electrodeposited metal to electrodeposit the electrodeposited metal in a cylindrical shape to a predetermined thickness on the rotating rotating shaft; When the electrodeposited metal has been electrodeposited to a predetermined thickness, the rotating shaft is removed from the electrolytic bath, and only the electrodeposited metal portion is pulled out from the rotating shaft. Metal cylinder forming method. 2) An electrolytic cell containing an electrolytic solution, a cathode rotating shaft at least partially immersed in the electrolytic solution and driven to rotate, an electrodeposited metal immersed and used as an anode, and an electrodeposited metal for supporting the rotating shaft. A high-purity metal cylindrical body forming apparatus comprising a rotating shaft support means, a rotational drive means for rotating the rotating shaft, and a power supply for supplying electricity between the rotating shaft and the electrodeposited metal.